Textile printing



Patented Aug. 24, 1 93? UNITED STATES TEXTILE PRINTING Samuel Howard andAlec Worm'ald, Blackley,

Manchester, England, assignors to Imperial- Ohemical Industries Limited,a corporation of Great Britain No Drawing. Application February 11,1935,

Serial No; 6,131. ary 19, 1934 9 Claims.

This invention relates to textile printing. More particularly, thisinvention deals with the printing of textile material, such as cottonfabric, with vat dyestuffs. By the term printing hereinafter wemean toembrace all processes, such as printing, padding, spraying, stencillingor otherwise applying color to fabric in areas of spe-- cial design.

It is an object of this invention -to provide a 10 novel process andreagents for producing resist styles, that .is areas where the fabricopposes the adsorption of color. Other and further important objects ofthis invention will appear as the description proceeds.

We have found that cotton fabric or other textile materials having anaffinity for leuco-esters of vat dyestuffs will develop local resistancetoward such dyestuffs if printed first with a composition comprising asalt of an organic compound as more fully defined below. Thispreprinting step is in general the same as the process known as resistprinting, and the composition mentioned may be of the usual type used insuch cases, comprising a gum adapted to cause adherence, water and thespecial assistants or resisting agents above referred to.

The novel efiect of this invention is that the resisting effect of theorganic salts employed by us is greater than by the assistants generally30 used heretofore, the resist-areas developing into a substantiallyclear white, exposing the original uncolored material.- Also, our novelassistants are successful in many cases where resist-effects haveheretofore been impossible or difficult to 35 obtain. This effect isparticularly brought out in the case of the sulfuric acid esters ofleuco-vat dyestuffs of the anthraquinone series, known generically asthe "-Soledons. These esters have great 'aflinity for cotton fabric andare on this 40 account difficult to resist to a clear white.

The novel assistants above referred to, and useful for this invention,are water-soluble salts of organic bases, or quaternary ammonium,phosphonium or sulfonium compounds, containing in their structure asaturated or unsaturated long-- In Great Britain Februthis respect, thisgroup of assistants contrasts with ordinary soaps, such as sodiumstearate,

palmitate or oleate, in which the organic radical is the anion, whilethecation is inorganic.

More specifically, the assistants useful for our invention may be saltsof primary, secondary or tertiary amines, quaternary ammonium compounds,salts of heterocyclic organic bases, or quaternary phosphonium orsulfonium compounds. The organic radical may contain an open chain of.at least Scarbon atoms, or it may contain the'benzyl or other aralkylgroups.

The following table and examples will further illustrate the types ofcompounds which we have found applicable for our purpose, but it should'be understood that our invention is by no means limited to thesespecific illustrations. In the examples which follow, the partsmentioned are by weightz' Derivatives of ammonia:

Aniline hydrochloride Dimethyl-aniline-hydrochlorideDimethyl-benzyl-phenyl-ammonium chlorideTetramethyl-diamino-diphenyl-ketonimine Derivatives of heterocyclicbases:

Oleic acid ester of N-hydroxyethyl-pyridin ium chloride Cetyl ether ofN-hydroxymethyl-pyridinium chloride Derivatives of sulfur:

. Cetyl-dimethyl-sulfonium methyl-sulfate Benzyl-cetyl-methyl-sulfoniummethyl-sulfate Dodecyl-dimethyl-sulfonium bromideBenzyl-methyl-dodecyl-sulfonium chloride Benzyl-ethyl-decyl-sulfoniumchloride Benzyl-methyl-dodecyl-sulfonium methylsulfate 9,090,890Derivatives of phosphorus: Example II cetyLmmethyl phosphonium biomideCotton cloth is printed with the following Dodecyl-trimethyl-phosphoniumbromide paste: Parts Some of the above are novel compounds, and Britishgum (40% solution) 60 are described more fully and claimed in copend-Water 30 ing applications Serial Nos. 611,236, 28,013 and 47,470. Theirgeneral schemes of synthesis, however, may be illustrated briefly by thefollowing examples.

Dimethyl-dicetyl-ammonium bromide may be prepared by reacting oneequivalent of dimethylamine and two equivalents of cetyl bromide.Dimethylcetyl-sulphonium methyl-sulfate may be prepared by treatingcetyl bromide with sodium hydrosulfide in alcohol, subjecting themercaptan thus formed to an alkylation treatment with dimethyl-sulfateand caustic sodafland thereafter obtaining the salt by treatment withdimethylsulfate .alone. Benzylmethyldodecyl-sulfonium methyl-sulfate isobtained by treating the mercaptan derived from dodecyl bromide with amixture of sodium ethoxide and benzyl chloride and finally treating theresulting product with dimethyl-sulfate.

Benzylcetylmethylsulfonium methyl-sulfate is madeby treating cetylmercaptan with sodium in methanol and then heating with benzyl chloride;the resulting cetyl benzyl mercaptan is then heated with dimethylsulfate. Dodecyldimethylsulfonium bromide is made by heatingdodecylmethyl sulfide with methyl bromide until a completelywater-soluble product is obtained;

dodecyl methyl sulfide is itself made by interacting equivalentquantities of dodecyl mercaptan and dimethyl sulfate in aqueous alkalinemedium. Benzylmethyldodecylsulfonium chloride is made by heating dodecylmethyl-sulfide with benzyl chloride until a completely watersolublecompound is produced.

Cetyl-trimethyl-phosphonium bromide may be prepared by interactingtrimethylphosphine and cetyl bromide: and dodecyltrimethylphosphoniumbromide may similarly be made from dodecyl bromide andtrimethylphosphine.

Ezample I Cotton cloth is printed with the renewing 0 paste:

I Parts British gum (40% solution) 65 Water 30 Benzylpyridinium chloride5 The printed material is dried and then overprinted with the followingpaste:

Soledon jade green (sulfuric ester of leucodimethoxy-dlbenzanthrone;Color Index No. 1101) 500 paste 2.5 Water l 25 5 Neutral starchtragacanth thickening--- 70 vSodium nitrite (30% solution) 2.5

Parts 7 Dimethylbenzylphenylammonium chloride 10 100 The printedmaterial is dried and overprinted with a paste consisting of PartsSoledon Brilliant Purple 2R (leuco ester of dichloro-isodibenzanthrone;Color Index No. 1104) v200 paste 5 Water 12 Diethylene glycol 8 Neutralstarch tragacanth thickening Ammonium sulfocyanide (50% solution) 6Sodium chlorate (10% solution) 8 Ammonium vanadate (1% solution) 1Example IV Cotton cloth is printed with the following paste:

Parts British gum (40% solution) Water 30 Benzylpyridinium chloride 5The printed material is dried and padded in a solution containing:

Parts Soledon orange 4R8 (leuco ester of dibromopyranthrone; Color IndexNo. 1098) paste--- 50 Water 1000 Sodium nitrite (30% solution) 25 Thepadded material is dried and developed -by passing at 60 C. through abath containing 20 parts of sulfuric acid (168 Tw.) per 1000 parts ofwater, washed and soaped for 5 to 10 minutes at the boil.

Example V Cotton cloth is printed with the following paste:

Parts British gum (40% solution) 60 Water 35 Cetyltrimethylammoniumbromide 5 The cloth is dried and overprinted with the following paste:

Parts Soledon jade green (6% solution) 5 Sodium nitrite 5 Neutral starchtragacanth thickening 60 Water 30 2,oao,sco 3 The neutral starchtragacanth thickening is made by dissolving 225 parts of wheat starch in1500 parts of boiling water and mixing the. paste with 1000 parts of 8%gum tragacanth.

The cloth is then steamed for 5 minutes, passed through a 2% solution ofsulfuric acid (168 Tw.) at' 60 c., rinsed in water, boiled in a l% soapsolution for minutes, rinsed in water and dried. A clean white resist ona green ground is obtained.

The cloth is dried and padded for 5 seconds at 60 C., in a solutioncontaining 7 parts of 9.10% aqueous paste of the sulfuric star ofCaledon yellow G. (Color Index No. 1118), 5 parts of sodium nitrite, and1000 parts of water.

' The cloth is squeezed, passed through a 2% solution of sulfuric acid(168 Tw.) for 2 minutes at 60 C., rinsed, boiled in a 1% s'oap solutionfor 10 minutes, rinsed' and dried. T

ExampleVII Cotton cloth is printed with the following aste: l'

British gumsolution) 60 Water 25 Dimethylcetylsulfonium /methyl-sulfate15 4 The printed material is dried, and then overprinted with thefollowing paste:

a Pal-tsv Soledon jade green XS paste 2.5 Water 25,

Neutral starclf tragacanth thickening '10 Sodium nitrite (30% solution)2.5

The overprinted material is dried and developed by passing at 60 C.through a bathcontaining 20 parts of sulfuric acid (168 'rw.) per 1000parts of water washedand soaped for 5 minutes at the boil. A whiteresist is obtained on a green e Example VIII Cotton cloth printed withthe, resist paste, as

in Example vn, is driedand padded an the following solution:

' Parts Soledon yellow GS (leuco ester offlavahthrone; Color Index No.1118) paste 3 Sodium nitri 5 5 Water 1000 The cloth is squeezed, theniieveloped and finished as in Example VII. Awhite resist 'is ob- 'tainedon a yellow ground;

[Example IX Cotton is printed with the following paste:-

Parts British gum r 60 ter I 35 W8 Dodecyltriethylphosphonium bromide 5The printed material is dried and padded in the following solutionzvParts- S oledon jade green XS paste 20 Glycerine 20 5 Water r 1000 Gumti'agacanth 50 Sodium nitrite (30% solution) 20 dried and treated as inExample VII.

Dodecyl triethylphosphonium bromide may be' prepared by reactingtriethylphosphine with dodecyl bromldein ethereal solution at 80 C. to

14 hours.

It will'be understood that our invention is 15 susceptible of widevariation in practice without departing from the spirit of thisinvention.

. It will be further understood that we selected for the purpose ofillustration leuco-esters of vat dyes merely because thesehave greatafiinity for 20 cotton fabric and are therefore particularly difficultto' resist to a clear white. The effects of our novel assistants aretherefore best brought out by the use of this typeof dyestufi. 'It isobvious, therefore, that good resistefiects may be 25 obtained alsowhere the dyestufl does not have any superior affinity for the fabric,for instance, in coloringcotton with a mixture of a vat "dyestuff inordinary quinone form and the usual reducing agents such ashydrosulflte, rongalite, 30

formopon, etc.

I We claim: 1. The-process of resisting cotton against coloration byleuco-esters of vat dyestuffs which have great affinity for cotton,which comprises apply- 35 ing to'the'same locally a printing gumcompris- 7 ing a water-soluble organic salt of an inorganic acid chosenfrom the group consisting of organic ammonium compounds. organicphospho'nium compounds and organic sulfonium compounds,

each of which contains an organic radicle of at least 6 carbon atoms butno ionizable substituents which would impart to said radiclean anioniccharacter. I t f 2. The process of producing colored designs upon'cottonfabric which comprises printing said fabric locally with a printingpaste comprising a salt of an organic nitrogenous base and inorganicacid, the organic portion of said nitrogenous base being characterizedby possessing at least 6 car-- 5 bon atoms and being free of anionicsubstituents then applying to said fabric a sulfuric acid ester of aleuco-anthraquinone vat color, and then developing the color and resistpatterns.

' 3. The process of producing colored designs 55 upon cottonfabric'wh'ich comprises printing said fabric locally with a printingpaste comprisinga salt of an inorganic acid and a quaternary organicheterocyclic nitrogenous-base free from anion-forming ionizablesubstituents-then apply- 3 ing to said fabric a sulfuric acid ester of aleuco- .anthrafiuinone vatdyestuff, developing the color pattern byhydrolysis and oxidation, and washing outthe resist pattern. a

4. The process of producing colored designs upon cotton: fabric whichcomprises printing said fabriclocally with a printing paste comprising asalt of an inorganic acid and tertiary organic sulfonium compound, thenapplying to said fabric a-sulfuric-acid esteroi' a 'leuco anthraquinonevat dyestuif, developing the color pattern by hydroly-- sis andoxidation, and washing out the resist pattern 5. The processof'producing colored designs upon cotton fabric which comprises printingsaid fabric locally with a printing paste comprising a salt of aninorganic acid and a quaternary or- 'ganic phosphonium compound, thenapplying to said fabric a sulfuric acid ester of a leuco-anthraquinonevat dyestuii', developing the color pattern by hydrolysis and oxidation,and washing out the resist pattern.

6. The process of producing white resists on cellulosic fabric undersulfuric esters of leuco vat dyestuffs which have a strong aflinity forcotton,

which comprises printing said fabric with a resist 20 which comprisesprinting said fabric with a resist paste containing a quaternaryammonium halide white resists against such leuco-esters of vat dyestuffsof the anthraquinone series which are dlill-' cult to resist by ordinarymethods, which comprises printing said fabric with a resist pastecontaining dimethyl phenyl benzyl ammonium chloride, then applying tothe fabric a leuco-ester of. a vat dyestuif, and developing the color.

9. The process of producing upon cotton fabric white resists against thesulfuric acid ester of leuco-dimethoxy-dibenzanthrone, which comprisesprinting said fabric with a resist paste containingdimethyl-pheny1-benzyL-ammonium chloride, then applying said color anddeveloping the same upon the fiber.

SAMUEL HOWARD. ALEC WORMALD.

